Substituted 1, 3, 5, 7-tetraalkyl-2, 6, 9-trioxa-10-phosphatricyclo [3.3.1.1.3,7] decanes



United States Patent 3,026,327 SUBSTITUTED1,3,5,7-TETRAALKYL-2,6,9-TRIOXA- -PH0SPHATRICYCL0[3.3.1.1 qDECANEsMartin Epstein and Sheldon A. Buckler, Stamford, Conn.,

assignors to American Cyanamid Company, New York,

N.Y., a corporation of Maine No Drawing. Filed July 6, 1960, Ser. No.41,028 11 Claims. (Cl. 260340.7)

The present invention relates to novel derivatives of 1,3,5,7 tetraalkyl2,6,9 trioxa 1O phosphatricyclo[3-3-1-1 ]decanes and methods ofpreparing same.

The 1,3,5,7 tetraalkyl 2,6,9 trioxa 10 phosphatricyclo[3-3-1-1 ]decanereactants used to prepare the novel derivatives contemplated herein areprepared as described in copending U.S. Application Serial No. 41,- 027filed simultaneously herewith on July 6, 1960.

According to a particular embodiment of said copending application,phosphine is reacted with 2,4-pentanedione in the presence ofhydrochloric acid to yield 1,3,5,7 tetramethyl 2,6,9 trioxa 10phosphatricyclo [3 3 1 1 decane as follows:

Generically, the reactants are represented by the following formula3,026,327 Patented Mar. 20, 1962 wherein R is H or the residue of aprimary phosphine; R is a member selected from the group consisting ofCF and lower alkyl; R R and R respectively, likewise each represent amember selected from the group consisting of CE, and lower alkyl.

As indicated by the equations given above, the R moiety in the generalformula just given is derived from phosphine or a primary phosphine (RPHreactant.

Typical primary phosphine reactants useful for preparing compounds ofthe general formula given above are phenylphosphine, methylphosphine,ethylphosphine, butylphosphine, octylphosphine, cyclohexylphosphine,dodecylphosphine, isopropylphosphine, allylphosphine, 2-hydroxyethylphosphine, benzylphosphine, para-chlorophenylphosphine,isobutylphosphine, 2-carboethoxyethylphosphine, 2-cyanoethylphosphine,and the like. It follows from the above listing that typicalsubstituents are those which do not enter into the reaction, which areinert under the conditions of the reaction, such as nitrile,

lower alkoxy, halogen, hydroxy, carboalkoxy (lower), and the like.

Typical fl-diketones useful for preparing the reactants of the presentinvention pursuant to copending application Serial No. 41,027, arehexafiuoro-substituted pentanediones, such as 1,1,1,5,5,5 hexafluoro2,4- pentanedione, 2,4-pentanedione, 3,5-heptanedione, 2,4- hexanedione,4,6-nonanedione, 5,7-undecanedione, and other like alkyl (C C)fl-diketones.

The fl-diketones and phosphines are brought together at a temperature inthe range of -20C. to 200 C preferably 15 C. to C.

Stoichiometric amounts of the reactants are generally employed, e.g.,one molar equivalent of the phosphine or primary phosphine reacts withtwo molar equivalents of the alkyl-p-diketone reactant to produce thecorresponding decane product.

The reactants are best brought together in the presence of a mineralacid, such as HCl, H 80 HBr, H PO HNO HI, or the like. Inert organicacids may be employed, such as methanesulfonic acid, benzeuesulfonicacid, benzenephosphonic acid, or the like.

By the same token, the reactions may be carried out in an aqueousmedium; an alcohol medium, such as that of ethyl alcohol, methylalcohol; an ether medium, such as that of diethylether, dioxane,tetrahydrofuran; a hydrocarbon medium, such as that of benzene, xylene,toluene, hexane; an acetone medium; and the like. As is evident,numerous inert organic solvents may be employed. By inert is meant thatthe solvents under the conditions of the reaction do not react to anysubstantial degree with the reactants and their products, and inaddition are inert with respect to the strong inorganic and organicacids employed in the reaction.

Several typical reactions demonstrating the preparation of the reactantscontemplated herein are given in the alphabetical series of examples,infra.

The novel products of the present invention are derived, as will be seenhereinafter, from the reactants represented access? the generic :Iormula I, above. These products have the general formula wherein 'R'--Rare the same as in reactant formula I, above, and Z'represents wherein[o is o 61s n 'Rbis ha gen, hydro en, or the residue of'aprimaryphosphine, 'i.e.,thesame as R as in the reactant form la;

Rcl

"wherein Re is on lid-'0- and substituted cai'bamoyl,

Rt bailing 'flie .hie nifissl isa we r ether ni 'is't'ituents'for'thephenyl'moiety being selected from the group consisting of halo-,fiitrd,an d'ldvv'er alkyl;

wherein Rf and Rg, respectively, represent H or lower alkyl and Y is theanion of a mineral acid; and

wherein Rh and Ri, respectively, represent lower alkyl and X is halide.

The acids derived from reactant I, above, are produced by the oxidationof the secondary phosphine reactant HP I with an organic or inorganicoxidizing agent, such as H 0 ozone, sodium hypochlorite,t-butylhydroperox- 'ide, and the like. The reaction is generally carriedout at a temperature in the range of C. to 250 C., or greater, in thepresence of a suitable inert solvent, such as H O, an ether, an alcohol,a hydrocarbon, e.g., benzene,

or the like. Sufficient oxidizing agent is employed to add 2 atoms ofoxygen to'the secondary phosphine reactant I The thioacids 'are preparedby bringing the secondary phosphine reactant I intocontact withelemental sulfur,

:in one of its various forms, asithe'okidi zi'n'g agent. Reaction isgenerally made to take place in the presence "ofan 'i'nert solvent, suchas 'a hydrocarbon, an ether, or the like. As in the case of the'oxoacids sufiicient'sulfur is used to provide at least Zatoms of'sulfurper. mole of secondary phosphine reactant]. I p i k The salts of these'o'x'oand 121110- acids are readily prepared by the addition thereto ofthe corresponding alkali, such as NaQH, KO'H, NH OH,-Pb(OH) etc. Inother words, the acids are neutralized with the appropriate alkalireactant.

If desired, the neutral salts may be prepared in situ, i.e., in aone-step process, by combining the secondary phosphine reactant I withthe appropriate oxidizing agent and alkali and recovering thecorresponding salt.

The isocyanate derivatives of the secondary phosphine reactants Icontemplated herein are prepared by bringing together an organicisocyanat'e of diisocyanate and the appropriate secondary phosphinereactant I in the presence of a basic catalyst, such as a tertiaryamine. The reactants are brought together at a temperature in the rangeof 0 C. to C. Suitable inert organic solvents are aromatic hydrocarbons,aliphatic hydrocarbons, ethers, and the like.

The

(IJH "R l3 derivatives of the present invention are prepared by reactingby reacting at least 1 equivalent of benzaldehyde or a substitutedbenzaldehyde with a secondary phosphine reactant I in the presence of anacid catalyst, such as a mineral acid orasn'on organic acid, at atemperature in the rangeof 0C. to 150 C. Generally, an inert sol- .vent,such as an alcohol, an'etherja hydrocarbon, or the like, is employed.

The

for this reaction are alcohols, ethers, hydrocarbons, or the like.

In the case where Rb is the residue of a primary phosphme, thecorresponding tertiary phosphine reactant I is employed under the sameconditions, with the exception that more than 1 molar equivalent ofoxidizing agent per molar equivalent of tertiary phosphine reactant Imay be employed.

When Rb is halogen and Q is oxygen, these products are prepared bybringing together the corresponding oxoacid (prepared as describedhereinabove) and thionyl chloride at a temperature in the range of C. to150 C. in the presence of an inert solvent, such as an ether, a.hydrocarbon, or the like.

To prepare the thio-analog the reaction is carried out in the samemanner With the exception that the secondary dithio-acid reactant isemployed and thionyl chloride is substituted with sulfuryl chloride.

The

OH let-( 311 RgGH 6H derivative compounds are prepared by reacting asecondary phosphine reactant I with at least 2 molar equivalents of alower alkyl aldehyde in the presence of an acidic catalyst, such as astrong mineral acid or strong organic acid. The reaction is generallymade to take place at a temperature in the range of 0 C. to 150 C. andusually in the presence of an inert solvent, such as an alcohol, anether, a hydrocarbon, or the like.

The

derivatives are prepared by bringing together. into reactive contact asecondary or tertiary phosphine reactant I with a lower alkyl halide ata temperature in the range of 0 C. to 200 C. and, preferably, in thepresence of an inert solvent, such as an alcohol, an ether, ahydrocarbon, or the like.

By inert solvent hereinabove is intended a solvent which under theconditions of the reaction does not react to any substantial degree withthe reactants or their reaction products.

The novel 1,3,5,7-tetraalkyl-2,6,9-t1ioxa-10-phosphatriclo [3-3-1-1decane derivatives of the present invention have utility as gasolineadditives. For example, up to about 10 milliliters of any one of thesederivatives, when dissolved in one gallon of gasoline, affordsprotection against misfiring, surface ignition, and the like.

The process for preparing the novel and useful derivatives of theinstant discovery will best be understood from the following examples:

EXAMPLE I 1 ,3 ,5 ,7-T e tramethy l-2,6 ,9-Tri0xa-1 O-Phosphatricyclo [33 1 1 ]Decane-10-In0ic Acid To a solution of 6.4 grams of1,3,5,7-tetramethyl-2,6,9- trioxa-lO-phosphatricyclo[3-3-1-1 ]decane(0.03 mole) in 25 milliliters of methanol is added 9.3 grams of 30percent hydrogen peroxide (0.08 mole) and the resulting solutionrefluxed for /2 hour. The methanol is evaporated to give 6.0 grams of1,3,5,7-tetramethyl-2,6,9-trioxaltl-phosphatricyclo[3-3-1-1decane-lO-inoic acid as a crystalline solid (81 percent yield). Ananalytical sample is prepared by recrystallization from isopropanol,melting point 222 C.

P, 12.48; molecular weight, 248. Found: C, 48.53; H, 6.91; P, 12.43;molecular weight, 254.

EXAMPLE II 1,3,5,7,10,10-Hexamethyl-2,6,9-Tri0xa-10-Phosphonia- Tricyclo[3 '3 1 1 Decane Iodide A solution of 2.1 grams of1,3,5,7-tetramethyl-2,6,9- trioxa-lO-phosphatricyclo[3 '3 1 1 decane(0.01 mole) dissolved in 30 milliliters of methyliodide is refluxed for18 hours. A solid precipitates and is collected and recrystallized fromacetone to yield 1.8 grams of1,3,5,7,10,10hexamethyl-2,6,9-trioxa-10-phosphonia tricyclo[3-3-l-1]decane iodide (48 percent yield). An analytical sample is prepared byrecrystallization from isopropanol, melting point 243 C.244 C.

Analysis calculated for C H O PI: C, 38.72; H, 5.96; P, 8.32; I, 34.10.Found: C, 38.57; H, 5.95; P, 8.04; I, 34.07.

EXAMPLE HI 1,3,5,7-Tetramethyl-10,10-Dibutyl-2,6,9-Tri0xa-10-Phosphoniatricyclo [3 3 1 1 Decane Iodide A solution of 5.3 grams of1,3,5,7-tetramethyl-2,6,9- trioxa 10 phosphatricyclo[3-3-1-l ]decane(0.025 mole) dissolved in 30 milliliters of butyliodide is heated to 65C. for 24 hours. A solid separates which is collected and recrystallizedfrom tetranydrofuran to yield an analytical sample of1,3,5,7-tetramethyl-10,10-dibutyl- 2,6,9 trioxa-IO-phosphoniatricyclo[3-3 '1- 1 decane iodide, melting point 209 C.211 C.

Analysis calculated for C H O IP: C, 47.37; H, 7.51; P, 6.79; I, 27.81.Found: C, 47.77; H, 7.97; P, 6.58; I, 27.41.

EXAMPLE IV 1,3,5] T etramethyl 10,10 Dihydroxymethyl 2,6,9-

T rioxa '10 Phosphoniatrz'cyclo [3-3-1-1 Decane Chloride A solution of6.0 grams of 1,3,5,7-tetramethy1-2,6,9- trioxa-lOphosphatricyclo[3-3-1-1 decane (0.027 mole), 4.9 grams of 37 percentformaldehyde (0.06 mole), 50 milliliters of methanol and 6 millilitersof concentrated hydrochloric acid is allowed to stand for 3 days under anitrogen atmosphere. The solvent is evaporated and the residuetriturated with acetone to precipitate 5.2 grams of a white solid,melting point 161 C.-162 C. A pure sample of 1,3,5,7-tetramethyl- 10,10dihydroxymethyl 2,6,9 trioxa 10 phosphonia tricycle [3'3-1-1 ]decanechloride (61 percent yield) is obtained by recrystallization fromacetone, melting point 16l-162 C.

Analysis calculated for C H O PCl: C, 46.08; H, 7.09; P, 9.91; C1,11.34. Found: C, 45.79; H, 7.20; P, 10.01; Cl, 11.39.

EXAMPLE V 1,3,5,7-Tetramethyl-10-Phenylcarbamoyl-Z,6,9-Tri0xa-IO-Phosphatricyclo [3 '3 1 1 ]Decane A solution of 4.0 grams of1,3,5,7-Tetramethyl-2,6,9- trioxa 10 phosphatricyclo[3-3-l-1 decane(0.019 mole), 2.3 grams of phenylisocyanate (0.02 mole), 50 millilitersof benzene and 0.5 gram of triethylenedi-amine is allowed to stand for24 hours undera nitrogen atmosphere. The solvent is evaporated and theresidue recrystallized from n-hexane to yield 3.7 grams of l,3,5,7-tetramethyl 10 phenylcarbamoyl 2,6,9 trioxa 10- phosphatricyclo[3-3l-ljdecane (58 percent yield), melting point 98 C.102 C. An analyticalsample is recrystallized from n-hexane, melting point, 108 C.- 109 C.

Analysis calculated for C H O PN: C, 60.89; H, 6.61; P, 9.24; N, 4.18...Found: C, 60.49; H, 6.91; P,

Analysis calculated for C1QH1705PZ C, 48.39; H, 6.90; 9.17; N, 4.25.

EXAMPLE vr N,N' (4-Methyl-m-Phenylene)-bis(1,3,5,7 Ttramthyl- 10Carboxamide 2,6,9 Trioxa 10 Phosphatricyclo '3'. i z lD cane) A solutionof 11.0 grams of l,3,5,7-tetramethyl-2,6,9- trioxa 10phosphatricyclo[3-3-1-1 decane (0.051 mole), 4.4 grams oftoluene-2,4.diisocyanate (0.025 mole), 20 milliliters of benzene and 0.2gram of triethylenediamine is allowed to stand for 3 days under anitrogen atmosphere. The solid (9.0 grams) that precipitates iscollected and identified as N,N-(4-methyl-mphenylene) bis('1,3,5,7-tetramethy1 10 carboxamide- 2,6,9 trioxa 10 phosphatricyclo[3-3-1-ldecane) (59 percent yield), melting point, 208 C.211 C. An analyticalsample is recrystallized from acetonitrile, melting point 217 C-2l9 .0.

Analysis calculated for C H O P N C, 57.42; H, 6.65; P, 10.21; N, 4.62.Found: C, 57.41; H, 6.81; P, 10.13; N, 4.75.

EXAMPLE VII 1,3,5,7 T etramethyl 2,6,9 Trioxa-IO-Phosphatricycl [3 3-1-1lDcane-IO-Dithioinoic Acid; Ammonium Salt -A solution of 4.0 grams ofl,3,5,7-tetramethyl-2,6,9- trioxa phosphatricyclo[3-3-1-1 decane (0.019mole), 1.2 grams of sulfur (0.038 mole),.18 milliliters of ammoniumhydroxide, 1 8, milliliters of water and 25 milliliters of methanolisrefluxed for three hours. The mixture is filtered and evaporated atreduced pressure to leave a gummy white solid. The solid is trituratedwith ethyl acetate to yield 4.6 grams of 1,3,5,7-tetramethyl 2,6,9trioxa 10 phosphatricyclo[3-3-1- 1 decane-I-O-dithi inoic acid, ammoniumsalt in 84 percent yield. analytical sample is recrystallized fromethanol and acetonitrile, melting point 217 C.218" C.

Analysis calculated for C H NO S P: C, 40.39; H,

16.78; N, 4.71; s, 21.57; P, 10.42. Found: c, 39.66; H,

EXAMPLE VHI 1,3,5,7-Tetramethyl-IO-Isobutyl-2,6,9-Trixa-10-Phosphqtricyclo [3 '3 1 1 ]Decane-10-Oxide EXAMPLE IX 1,3,5,7,10-Pentamethyl-10-Isobutyl-2,6,9-Tri0xa@10- Phosphoniatricyclo [3 '3 1 l]Decane Iodide A solution of 1.6 grams of 1,3,5,7-tetramethyl-10-.isobutyl 2,6,9 trioxa 10 phosphatricyclo[3-3-l-1 decane (0.006 mole)and 10 milliliters of methyliodide is allowed to standfor 3 days. Asolid precipitates and it is collected and recrystallized from acetoneto yield an analytical sample of 1,3,5,7,lO-pentamethyl-lO-isobutyl2,6,9 trioxa 10 phosphoniatricyclo[3 31- 1 decane iodide, melting point202 C.203 C.

Analysis calculated for C H O IP: C, 43.49; H, 6.81; I, 30.64; P, 7.48.Found: C, 43.65; H, 6.58; I, 30.81; P, 7.27.

8 EXAMPLE X,

1,3,5,7-TetramethyZ-IO-a-Hydmxybenzyl-2,6,9-Trioxa- 10-Phosphatricycl0[3 '3 1 1 Decane A solution of 4.5 grams of 1,3,5,7-tetramethyl-2,6,9-trioxa-lO-phosphatricyclo[3 -3 l 1 decane (0.02 mole), 55 milliliters ofmethanol, 3 milliliters of concentrated I-ICl and 4.5 grams ofbenzaldehyde (0.053 mole) is allowed to stand at room temperature for 2hours, during which time a solid precipitates. 6.4 grams of 1,3,5,7-tetramethyl 10 a hydroxybenzyl 2,6,9 trioxa 10- phosphatricyclo[3-3-1-1"]decane is collected, melting point 128 C.-132 C. An analytical sampleis prepared by recrystallization from methanolwater, melting pointAnalysis calculated for C H O P: C, 63.34; H, 7.19; P, 9.61. Found: C,63.64; H, 7.48; P, 9.30.

- EXAMPLE X[ 1,3,5,7-Tetramethyl-2,6,9-Tri0xa-10-Phosphatricyclo- [3 '3-1 '1 TD'cane-1 O-Sulfide A solution of 5.0 grams of1,3,5,7-tetramethyl-2,6,9- tn'oxa 10 phosphatricyclo[3-3:1-l ]decane(0.023 mole), 0.74 gram of sulfur (0.023 mole) and 50 milliliters ofbenzene is refluxed for 2 hours. The solvent is evaporated at reducedpressure to leave a residue of 1,3,5,7- tetramethyl2,6,9-trioxa-10-phosphatricyclo[3 3 1 1 decane-lO-sulfide.

EXAMPLE XII 1,3,5,7-Tetramethyl-2,6,9-tri0xa-10-Phosphatricyclo- [3 '3'1 1 ]Decane-1O-Dithioinoic Acid A solution of 6.0 grams of.1,3,5,7-tetramethyl- 2,6,9- trioxa-10-phosphatricyclo[3-3-1-1 (0.027mole), 1.73 grams of sulfur (0.054 mole) and milliliters of benzene isrefluxed for 5 hours. The solvent is evaporated. The residue isl,3,5,7-tetramethyl-2,6,9-trioxa-lo-phosphatricyclo[3 -3 1 1]decane-10-dithioinoic acid.

EXAMPLE XIII 1,3,5,7-Tetrdm'ethyl-2,6,9-Tri0xa-10-Ph0sphatricycl0- V [3'3 -1 1 ]Decane-10-0xide To a solution of 6.4 grams of1,3,5,7-tetramethyl-2,6,9- trioxa-10 phosphatricyclo [3 3 1-1 ]decane(0.03 mole) dissolved in 50 milliliters of methanol is added 3.4 gramsof 30 percent hydrogen peroxide'(0.03 mole) and the resulting solutionallowedtostand for one hour. The solvent is evaporated to leave aresidue of 1,3,5,7-tetra methyl 2,6,9 trioxa 10 phosphatricyclo[3 -3-1-l.decane-lO-oxide which is. recrystallized'from n-heptane, .melting point172 C.l75 C.

EXAMPLE XIV 1,3,5,7-Tetramethyl-IO-Chl0r0-2,6,9-Tri0xa-10-Phosphatricyclo [3 -3 1 1 ]Decane-1 O-Oxide EXAMPLE XV1,3,5,7-Tetramethyl-10-Chl0r0-2,6,9-Trioxa-IO-Phosphazricyclo [3 3 1 -1]Decane-10-Sulfide A solution of 4.2 grams of 1,3,5,7-tetramethyl-2,6,9-trioxa 10. phosphatricyclo[3-3-l'1 decane 10 dithioinoic acid (0.015mole, product from Example XII), 4.1 grams of sulfuryl chloride (0.03mole) and 50 milliliters of benzene is refluxed for 3 hours. The mixtureis filtered toremovethe sulfur andthe filtrate evaporated to yield theproduct, 1,3,5,7-tetramethyl-l-chloro-2,6,9-'

trioxa phosphatn'cyc1o[3 3 l 1 decane-lO-sulfide.

EXAMPLE XVI 1,3,5,7-Tetramethyl-2,6,9-Trioxa-IO-Phosphalricyclm [3 '3 -1-1 "]Decane-10-In0ic Acid, Ethyl Ester A solution of 6.1 grams of1,3,5,7-tetramethyl-10- chloro 2,6,9 trioxa 10 phosphatricyclo[3-3-l-1decane-lO-oxide (0.023 mole, product from Example XIV), 2.1 grams ofanhydrous ethanol (0.046 mole), 1.9 grams of pyridine (0.024 mole) and50 milliliters of hexane is refluxed for 3 hours. The mixture isfiltered to remove the pyridine hydrochloride and the solvent evaporatedto yield the product l,3,5,7-tetramethyl-2,6,9- trioxa 10phosphatricyclo[3 -3 1 1 decane 10 inoic acid, ethyl ester.

EXAMPLE XVII 1,3,5,7-Tetramethyl-2,6,9-Trioxa-10-Phosphatricyclo- [3 '3-1 -l ]Decane-10-lnoic Acid, Sodium Salt To a solution of 2.48 grams ofl,3,5,7-tetramethyl-2,6,9- trioxa 10 phosphatricyc1o[3-3-1'1 ]decane l0-inoic acid (Example I) in 25 milliliters of water is added 0.4 gram ofsodium hydroxide. The solution is evaporated to dryness to give thewhite solid product, l,3,5,7- tetramethyl2,6,9-trioxa-l0-phosphatricyclo[3 3 1 1 decane-lO-inoic acid, sodiumsalt.

EXAMPLE XVIII 1,3,5] Tetra(Triflu0r0methyl) 2,6,9Trioxa-IO-Phosphatricycl0[3-3-l -1 ]Decane-10-Inoic Acid, Magnesium Sal!The procedure of Example XVII is repeated in every essential respect,except that 0.3 gram of magnesium hydroxide is used in place of sodiumhydroxide. The product is 1,3,5,7-tena(trifluoromethyl)-2,6,9-trioxa-10-phosphatricyclo[3-3-1-1 ]decane-10-inoic acid, magnesium salt.

EXAMPLE XIX 1,3,5] T etramethyl 2,6,9 Trioxa 10 Phosphatricyclo [3 -3-1-1 ]Decane 10 Dithioinoic Acid, Silver Salt trioxa 10phosphatricyclol3-3-l-l ldecane 10 dithioinoic acid, ammonium salt (0.01mole, product from Example VII) is dissolved in 25 milliliters of waterand 3.4 grams of silver nitrate (0.02 mole) is added. After standing for24 hours the product 1,3,5,7-tetramethyl- 2,6,9 trioxa 10phosphatricyclo[3-3-l-l ]decanelO-dithioinoic acid, silver salt isobtained by filtration.

EXAMPLE XX 1,3,5] Telraethyl 2,4,9 Trioxa 10 phosphatricyclo- [3 '3 -1]Decane-10-1n0ic Acid, Butyl Ester The procedure of Example XVI isrepeated in every essential respect using 7.4 grams ofl,3,5,7-tetraethyl-10- chloro 2,6,9 trioxa 10 phosphatricyclo[3-3-1- 1decane-lO-oxide and 3.4 grams of anhydrous n-butanol. The product is1,3,5,7-tetraethyl-2,4,9-trioxa-10-phosphatricyclo[3-3-1-1]decane-10-inoic acid, butyl ester.

EXAMPLE XXI 1,3,5] Tetrabutyl 10 Phenyl 2,6,9 T rioxa 10-Phosphatricyclo [3 -3 -1 ]Decane-10-Sulfide 1,3,5] Tetramelhyl 10 Chloro2,6,9 Trioxa 10- PhosphatricycloB 3 1 1 ]Decane To a solution of 4.3grams of 1,3,5,7-tetramethyl-2,6,9- trioxa-10-phosphatricyclo[3-3-l-1decane (0.02 mole) dissolved in 40 milliliters of methylene chloride at0 C., is added 2.0 grams of phosgene (0.02 mole) and the solutionallowed to stand for 24 hours. The solvent is evaporated to leave theproduct 1,3,5,7-tetramethyl-l0-chloro- 2,6,9-trioxa-10-phosphatricyclo[3 3 l 1 decane.

EXAMPLES XXIII-WV The following Tables I, II and HI are self-explanatoryA solution of 3.0 grams of 1,3,5,7-tetramethyl-2,6,9- .45 and theyfurther illustrate the present invention:

TABLE I 1 C\ 0 C32 11-]? Rr-C-O-C-Rg A B /O O C l.

Example R1 R2 R1 B4 A Solvent Time Temp. Procedure B (Hoursi C.

XXIII H OH CH nitrotoluene" 4 Example V 1,3,5.7-tetramethyl-10-(p-nitropl1enyl- H C I a 3 pheuylcarbamoyl)-2,6,9-trioxa-l0-phosphaisotricyclo[3-3-1-1 "ldeeane. cyanate.XXIV- OF; OF; OH; CH3 n-butylisobenzene 24 30 Example V 1,3-d1metl1yl-5,7-di-tr1fiuoromethyI-10- cyanate. butylcarbamoyl-2, 6, 9-tnoxa-10-phos-E V phaztrieyelotgbg-g & dglane. h l CH C m-chlorolene 6 xample 1,3,5,-tetrae y rnorop eny- XXV C2115 2 5 [E5 phenyl Ky carbamoyl)-2,6,9-trioxa-10-phosphaisoeya- V tricyclo[3-3-l-1 ]decane. nate. CH CHhe meth benzene. 10 50 ExampleVI. N,N-hexamethylene-bis(1,3,5,7- XXVI HCH: CH: 3 a l eiie (Hi5?)- tetramethyl 10-carb0xamide-2,6,9- cyanate. 1Erioxa-gO-phosphatricyelo[3-3-1 ecane H C H C H -chlorobenztetrah 6 40Example X 1,3,5,7- tetrabutyl- 10- (a-hydroxy-p XXVH 4 9 o P aldehyde.drochlorobenzyl)-2, e, Q-trioxa-ldphosfuran. E I X phatricycloB-g-l-l"]dt%ai1e1.0( h VIII F CF -tolualdeethanol. 4 30 xam e 1 3,5,7-tetra-triuorome y -ay XX OF: CF: 0 a 3 p hyde. p droxy-Pmethylbenzyl)-2,6,9-trioxa- IO-phosphatricyclo[3-3'1-1 ldecane.

lected iromthe group consisting of CP and lower alkyl; and Z is amember, selected from the group consisting of:

TABLE-II e H-.-P mjc o-c-n, 2A B 7 o ,7

E on, t 1' Example R1 R R3 R; A B Solvent Time Iemp.- 0

(Hours) C.

XXIX- CH; OH; OH; CH; acetaldehydeun HBr ethanol. 5l,3;5,7ttetramethyl-10,l0-bis,(l,--hydroxyethyl)'-'2,6,9 trioxa 10-phosphgniatr leyclo[3;31=1]decane bro- 7 1m 8-: XXX OF: CF; CF: CF;butyraldehydefi HNO methanol 16 62 1,35.7tetra-trifluoromethyl-10.10-bls a (1- hydroxybutyl) 2, ,9 trioxa -10-pligsphon'iatricyclo[3-3-l l -fidecane ni ate. XXXI 64H: 041-10 CiHnCQHQ proplonalde- .Hzisopropanol. 10 80 1,3,5] tetrabutyl 10,10 bis(1hyt r hyde. S04 droxypropyll-z6,9'-t1ioxal0?phosphoniatric'yclo {331 1 1decane hydrogensulfate.

TABLE'III 1 T O'.E\[: R-P R4CO-C-=B; 2A B O i---CH; v. 1

Example 31 R; R3 R4 R A Solvent 7 Time tram i B ,(Hours) CL XXXII CF,CFa Q'Fa t CF; H thyl mmide methanol-. 4 .60. 1,3,5,7-tetr -trifl 0r0mthyI-10 0- diethyl 2,6,9 trioxa 10- phosph onia tricycle {3-3-14 decanebromide. XXXIII ClH'n CAHQ 'C4HJ" 01H H methy c orideanol e 401,3,5;7-tet,rabuty 1 10,10 dimethyl- 2,6,9 trioxa IO-phosphioniatricycloV t V [3-3-14 decane chloride. XXXIV C 3 CH8 H: 6 5 PIOPYl b i propanol-8 60 1,3,5,7 tetramethyl 10 propyl 10 V V Vphenyl-2,6,9,-,trioxa-10-phosphoniatrit a eyc10{3,-3-1.-1 decanebromide; XXXV OF; CF: CF; CF DC'sbutyl chloride--- methanol... 6 6O1,3,5,7-tetra-trifluoromethyl-10-butyl- 11 lfl-octyl 2,6,9-trioxaIO-phosphonla tricyclo [3-3-1-1 decane chloride.

Clearly, the instant discovery encompasses numerous modifications withinthe skill of the art. Consequently, while the present invention has beendescribed in detail with respect to specific embodiments thereof, it isnot intended that these details be construed as limitations upon thescope of the invention, except insofar as they appear in the appendedclaims. 7

We claim: a a a i 1. A substituted 1,3,5,7-tetraalkyl2,6,9-trioxa-10=phosphatricyclo[3-3'1- 1 decane of the formula whereinR, R, R and R each represent a member se- -in-which Q is a memberselected from the group consisting of 0 and S and Ra is a memberselected from the group consisting of H, an alkali metal, ammonium, analkaline earth metal, and a heavy metal;

wherein 'Q is a member selected from the group consisting of O and S,and Rb is a memberselected iromthe $101 1 consisting of h o e y g r andthe residue of a primary phosphine;

whereinRc is a memb rselected'from the group consisting of OH. RHE- aand substituted carbamoyl,

Rd being a member selected from the group consisting of phenyl,halo-substituted phenyl and lower alkyl-substituted phenyl and Re isselected from the group consisting of lower alkyl, substituted alkyl,phenyl, substituted phenyl, said substituent on the 5 lower alkyl moietybeing alkyl and 20 wherein R and Rg each represent a member selectedfrom the group consisting of H and lower alkyl, and Y is the anion of amineral acid; and

wherein Rh and Ri each represent lower alkyl, and X is halo-' 2.1,3,5,7-tetramethyl 2,6,9-trioXa-10-phosphatricyclo- [3 3 1 l]decane-1O-inoic acid.

3. 1,3,5,7,10,l0-hexarnethyl-2,6-9 trioxa-lO-phosphoniatricyclo [3 3 1 1decane iodide.

4. 1,3,5,7 tetramethyl 10,10-dihydroxymethyl-2,6,9- trioxa l0phosphoniatricyclo[3-3-1-1 decane chloride.

5. 1,3,5,7-tetramethyl 1Ophenylcarbamoyl-2,6,9-trioxa-10-phosphatricyclo[3 3 1- 1 decane.

6. N,N (4-methyl-m-phenylene) bis(1,3,5,7tetramethyl-10-carboxamide-2,6,9-trioxa IO-phosphatricyclo- [3-3-1-1]decane).

7. 1,3,5,7-tetramethy1 2,6,9-tri0Xa-10-phosphatricyclo- [3-3 1 1]decane-lO-dithioinoic acid, ammonium salt.

8. l,3,5,7 tetramethyl 10 isobutyl 2,6,9-trioxa-10- phosphatricyclo [3 31- 1 ]decane-10-oXide.

9. 1,3,5,7,10-pentamethy1- 10 isobutyl 2,6,9-trioxa-10-phosphoniatricyclo [3 3 1 1 decane iodide.

10. l,3,5,7-tetramethyl 10cc-hydrOXybenZyI-Z,6,9-trioxa-lO-phosphatricyolo [3 3 1 1 ]decane.

11. 1,3,5,7-tetramethy1 2,6,9 trioxa-lO-phosphatricyclo-[3 -3 -1-1]decane-10-0xide.

No references cited.

UNITED STATES PATENT ICE CERTIFICATE OF CORRECTION Patent No. 3,026,327March 20, 1962 Martin Epstein et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below Column 1 lines 25 to 33, the formula should appear asshown below instead of as in the patent:

column 4, lines 61 to 64, for 13 Rd-P read Rb-P columns 9 and 10, TABLE"Example XXVI", under column B, line 12 thereof for 5.3. lo read [3-3 1'1- I Signed and sealed this 7th day of August 1962.

(SEAL) Attest:

'ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner ofPatents

1. A SUBSTITUTED 1,3,5,7-TETRAALKYL-2,6,9-TRIOXA-10-PHOSPHATRICYCLO(3.3.1.13,7) DECANE OF THE FORMULA